If I may use this oppourtunity to alter my list slightly:
Heroes:
1. Don Quixote
2. Atticus Finch (from To Kill a Mockingbird)
3. Ed Wood
4. JC Denton (from Deus Ex)
5. Captain Picard
Villains:
1. Salieri (from Amadeus)
2. Richard III
3. Big Brother (from 1984)
4. Livia and Caligula (from I, Claudius)
5. Malcolm Tucker (from The Thick of It)
I couldn't decide between Livia and Caligula. Livia poisons everyone she meets and, like Malcolm Tucker, pulls incredibly illegal strings to stay in power for as long as possible (though, Malcolm never murders anyone). And Caligula is completely insane. Like...imagine if the Joker was a Roman Emperor.
Seriously though, if you have any interest in television drama, watch I, Claudius. I have no idea how to describe it...just watch it.